U.S. patent number 3,969,298 [Application Number 05/522,071] was granted by the patent office on 1976-07-13 for selected lipophilic aminimides and polymers derived therefrom useful for making stable emulsions.
This patent grant is currently assigned to The Kendall Company. Invention is credited to Robert C. Gasman.
United States Patent |
3,969,298 |
Gasman |
July 13, 1976 |
Selected lipophilic aminimides and polymers derived therefrom
useful for making stable emulsions
Abstract
Lipophilic aminimides containing ethylenically-unsaturated
moieties and carboxylic acid groups are disclosed. These compounds
are useful as monomeric emulsion stabilizers, and may be
polymerized with various co-monomers to provide pressure-sensitive
adhesives.
Inventors: |
Gasman; Robert C. (Schaumberg,
IL) |
Assignee: |
The Kendall Company (Boston,
MA)
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Family
ID: |
27009567 |
Appl.
No.: |
05/522,071 |
Filed: |
November 8, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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381932 |
Aug 24, 1973 |
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120331 |
Mar 2, 1971 |
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Current U.S.
Class: |
524/813; 526/304;
526/312; 526/327; 526/329.4; 526/341; 526/219; 526/307; 526/320;
526/328; 526/329.3; 526/329.5; 526/344.2 |
Current CPC
Class: |
C08F
2/28 (20130101); C08F 246/00 (20130101); C09J
7/385 (20180101) |
Current International
Class: |
C08F
2/12 (20060101); C08F 2/28 (20060101); C08F
246/00 (20060101); C09J 7/02 (20060101); C08F
003/90 () |
Field of
Search: |
;260/8.3N,89.7R,29.6HN,78UA,29.6H,78.3UA |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Kulkosky; Peter F.
Attorney, Agent or Firm: Trevors; Ellen P.
Parent Case Text
This is a continuation, of application Ser. No. 381,932 filed Aug.
24, 1973, which is a divisional of application S.N. 120,331 filed
on Mar. 2, 1971.
Claims
What is claimed is:
1. A process for stabilizing the polymerization of
ethylenically-unsaturated monomers which comprises copolymerizing
in an aqueous medium with a free-radical inorganic or organic
percompound catalyst at least one compound having the formula
##EQU6## wherein each R is an independently selected alkyl having 1
to 3 carbon atoms and wherein
a. R.sub.1 is 4-hydroxymaleoyl, 4-hydroxyfumaroyl,
4-hydroxycitraconoyl or 4-hydroxyitaconoyl and R.sub.2 is a
lipophilic radical comprising an aliphatic hydrocarbon chain having
about 10 to about 28 carbon atoms; or
b. R.sub.1 is a lipopholic radical comprising an aliphatic
hydrocarbon chain covalently linked to the nitrogen through an
hydroxysuccinyl linkage and R.sub.2 is -A-V wherein A is ethylene,
propylene, isopropylene, 2-hydroxypropylene, acetoxypropylene or
-O-CH.sub.2 -CHR.sub.6 -(O-CH.sub.2 -CHR.sub.6).sub.n - where
R.sub.6 is hydrogen or methyl and n is zero to 4, and V is
acryloyloxy, methacryloyloxy, acrylamido, methacrylamido, vinyloxy,
allyloxy, methallyloxy, vinylacetoxy, allylacetoxy,
methallyloacetoxy, allyl, methallyl, 4-hydroxymaleoyloxy,
4-hydroxyfumaroyloxy, 4-hydroxycitraconoyloxy, or
4-hydroxyitaconoyloxy; with the proviso that A is zero where V is
vinylacetoxy, allylacetoxy, methallylacetoxy, allyl or methally,
with at least one ethylenically-unsaturated monomer selected from
the group consisting of vinyl chloride, vinyl acetate,
acrylonitrile and acrylic esters having the formula ##EQU7##
wherein R.sub.7 is hydrogen or methyl and R.sub.8 is C.sub.1 to
C.sub.18 alkyl.
2. The process of claim 1 wherein between about 1.0 and 30.0 weight
percent of A is copolymerized with between about 99.0 and about
70.0 weight percent of B.
3. An organic polymer which comprises a minor portion of at least
one compound A of claim 1 and a major portion of at least one
compound B of claim 1.
4. The polymer of claim 3 wherein compound A comprises from about 3
to about 30 weight percent of the copolymer.
5. The polymer of claim 3 wherein compound A is
1,1-dimethyl-1-p-dodecylbenzylamine-4-hydroxymaleoylimide and
compound B is a mixture of ethyl acrylate and 2-ethylhexyl
acrylate.
6. A stable, surfactant-free aqueous dispersion of the copolymer of
claim 3.
Description
This invention relates to selected lipophilic aminimides, to the
use of said lipophilic aminimides as monomeric emulsion stabilizers
for the polymerization of ethylenically-unsaturated monomers, to
pressure-sensitive adhesive polymers containing recurring units of
said lipophilic aminimides and to flexible sheet material having a
coating containing such pressure-sensitive adhesive polymers.
Various aminimides have been previously prepared and reported in
the literature. Thus, U.S. Pat. No. 3,410,880 discloses aminimides
containing aliphatic hydrocarbon radicals and their use in
detergent compositions, while U.S. Pat. Nos. 3,485,806 and
3,527,802 describe the preparation of selected aminimides
containing acryloyl or methacryloyl moieties.
Now it has been found that certain lipophilic aminimides containing
ethylenically-unsaturated moieties and lipophilic groups can be
provided according to this invention. More specifically these
lipophilic aminimides have the formula ##EQU1## wherein each R is
an independently selected alkyl moiety; and wherein
A. R.sub.1 is an ethylenically-unsaturated radical containing a
carboxylic acid group and R.sub.2 is a lipophilic radical
comprising an aliphatic hydrocarbon chain having at least about 10
carbon atoms; or
B. R.sub.1 is a lipophilic radical comprising a carboxylic acid
group and an aliphatic hydrocarbon chain and R.sub.2 is an
ethylenically-unsaturated radical.
It is a critical feature of the compounds of this invention that
they contain a selected lipophilic radical, an
ethylenically-unsaturated moiety, and a carboxylic acid group.
Thus, it has been found that the presence of the carboxylic acid
group is essential to the functioning of these compounds as
monomeric emulsion stabilizers. THe necessity of having a free
carboxylic acid group is surprising in view of the disclosure of
the aforementioned U.S. Pat. No. 3,485,806, which teaches that the
aminimides disclosed therein should be free of such acid
groups.
While any compound having the general formula I can be provided
according to this invention, preferred aminimides include those
compounds I wherein each R is an independently selected alkyl
having 1 to 3 carbon atoms and R.sub.1 and R.sub.2 are selected
from group a) wherein R.sub.1 is 4-hydroxymaleoyl or
4-hydroxyfumaroyl (HOCO-CH=CH-CO-), 4-hydroxycitraconoyl
(HOCO-CH=C(CH.sub.3)-CO-) or 4-hydroxyitaconoyl ##EQU2## and
R.sub.2 is a lipophilic radical comprising an aliphatic hydrocarbon
chain having about 10 to about 28 carbon atoms.
The term "aliphatic hydrocarbon chain" in the claims and
specification herein includes saturated, unsaturated,
straight-chain and branched groups.
By the term "lipophilic radical" in the case of R.sub.2 is meant an
aliphatic hydrocarbon chain covalently linked to the nitrogen
either directly or through an intermediate linkage as illustrated
below where L represents the aliphatic hydrocarbon chain: a benzyl
group, ##SPC1##
an ester or amide group such as -CH.sub.2 -CHR'-ACO-L wherein R' is
hydrogen or methyl and A is oxygen or -NH-; a polyalkylene oxide or
alkylene ether group such as -CH.sub.2 -CHR.sub.3 -(O-CH.sub.2
-CHR.sub.3).sub.n -OL wherein R.sub.3 is hydrogen or methyl and n
is zero to 4; an acetoxy or acetamido group such as -CH.sub.2
-CO-OL and -CH.sub.2 -CO-NHL; a hydroxysuccinyloxy or
hydroxysuccinylamino group having the formula -R.sub.4
-A-CO-CHL-CH.sub.2 -COOH wherein R.sub.4 is a diradical, preferably
ethylene, propylene, isopropylene, 2-hydroxypropylene,
acetoxypropylene, or -CH.sub.2 -CHR.sub.5 (O-CH.sub.2
-CHR.sub.5).sub.n - where R.sub.5 is hydrogen or methyl and n is
zero to 4, and A is oxygen or -NH-; and isomers of the
aforementioned hydroxysuccinyloxy or hydroxysuccinylamino groups
wherein the aliphatic hydrocarbon chain L is attached to the carbon
atom adjacent to the carboxyl group.
The aminimides having the formula I wherein R.sub.1 and R.sub.2 are
selected from group (a) can be readily provided by reacting a
stoichiometric amount of an appropriate substituted hydrazine with
a lipophilic halide followed by reaction with a suitable acid
anhydride. Illustrative hydrazines include unsymmetrical dimethyl
hydrazine, unsymmetrical diethyl hydrazine, unsymmetrical dipropyl
hydrazine, methyl ethyl hydrazine, etc.
Exemplificative lipophilic halides suitable for use in the
preparation of aminimides I includes decyl chloride, p-dodecyl
benzyl chloride, octadecyl chloride, octacosyl chloride, tridecyl
chloroacetate, dodecyl chloride, tetradecyl chloride, hexadecyl
chloride, undecyl bromide, tridecyl bromide, pentadecyl bromide,
heptadecyl bromide, oleyl bromide and the chloroacetamide
derivative of Primene 81R. The latter material, marketed by the
Rohm and Haas Company, is reported to be a mixture of t-alkyl
primary amines consisting principally of C.sub.11 to C.sub.14 alkyl
amines having highly branched alkyl groups in which the primary
amino nitrogen is directly attached to a tertiary carbon atom.
Preferably, mixtures of lipophilic halides having an average number
of carbon atoms between 10 and 28 are employed.
The acid anhydrides appropriate for use in the preparation of
compounds I are maleic anhydride, citraconic anhydride and itaconic
anhydride. Isomerization of the 4-hydroxymaleoyl compounds I
according to well-known techniques will provide the
4-hydroxyfumaroyl compounds. The aforementioned reaction to provide
the aminimides I can be carried out over a wide temperature range.
The first part of the reaction, i.e. the quaternization of the
hydrazine, is carried out at a temperature of about 60.degree.C to
120.degree.C, preferably 75.degree.-85.degree.C, while reaction of
the quaternized hydrazine with the anhydride can be effected at
temperatures of about 30.degree. to 80.degree.C, preferably
40.degree.-50.degree.C.
While the reaction proceeds satisfactorily in the absence of
solvents or diluents, an appropriate solvent can be advantageously
employed to insure continuance of the reaction in the liquid phase.
In the first stage of the reaction, diluents such as acetonitrile,
propionitrile, butyronitrile can be utilized, while alcohols such
as isopropanol and t-butanol can be employed in the second part of
the reaction.
An appropriate acid acceptor is used to generate the aminimide from
the hydrazonium salt. Such acid acceptors include methanolic sodium
methoxide, aqueous solutions of alkali or alkaline earth
hydroxides, anionic ion exchange resins, etc.
Other preferred aminimides are those compounds I wherein each R is
an independently selected alkyl having 1 to 3 carbon atoms and
R.sub.1 and R.sub.2 are selected from group b) wherein the
lipophilic radical R.sub.1 comprises an aliphatic hydrocarbon chain
covalently linked to the nitrogen through an hydroxysuccinyl
linkage, and the ethylenically-unsaturated radical R.sub.2 is a
radical containing a carbon to carbon double bond capable of
polymerization with other ethylenically unsaturated monomers, said
bond being one which is a terminal carbon to carbon double bond,
e.g. as in a vinyl radical, or one which is conjugated with the
double bond of a carbon to oxygen linkage, e.g. as in the alpha,
beta unsaturated dicarboxylic acids and acrylic and methacrylic
acids, and preferably where R.sub.2 is -A-V, as illustrated by the
following general formula wherein L is an aliphatic hydrocarbon
chain as previously described: ##EQU3## In the above formula, A is
ethylene, propylene, isopropylene, 2-hydroxypropylene,
acetoxypropylene or -O-CH.sub.2 -CHR.sub.6 (O-CH.sub.2
-CHR.sub.6).sub.n - where R.sub.6 is hydrogen or methyl and n is
zero to 4 and V is acryloyloxy, methacryloyloxy, acrylamido,
methacrylamido, vinyloxy, allyloxy, methallyloxy, vinylacetoxy,
allylacetoxy, methallylacetoxy, allyl, methallyl,
4-hydroxymaleoyloxy, 4-hydroxyfumaroyloxy, 4-hydroxycitraconoyloxy,
or 4-hydroxyitaconoyloxy; with the proviso that A is zero where V
is vinylacetoxy, allylacetoxy, methallylacetoxy, allyl or
methallyl. Isomers of the above compounds wherein the aliphatic
hydrocarbon chain L is attached to the carbon atom adjacent to the
carbonyl group in the hydroxysuccinyl linkage are also included in
the scope of this invention.
Compounds having the above formula are readily provided by reacting
a vinyl monomer containing an active halogen or an oxirane group,
i.e. a compound of the formula V-A-X wherein V and A are as
previously described and X is halogen or oxirane, with one of the
aforementioned substituted hydrazines followed by reaction with a
succinic anhydride having the following formula wherein L is as
previously described: ##EQU4## Representative vinyl monomers having
the formula V-A-X include 2-bromoethyl acrylate, glycidyl acrylate,
4-hydroxymaleoyloxyethylene chloride, 2-chloroethylacrylamide,
allyl chloroacetate, methallyl chloroacetate, acryloyloxypropenyl
chloride, 3-methyacryloyloxy, 2-hydroxypropylene chloride,
acryloyloxydi (ethylenoxy) ethylene chloride, allyl bromide,
methallyl chloride, etc. The reaction conditions, i.e. temperature,
diluents, etc. are similar to those described for the preparation
of compounds I wherein R.sub.1 and R.sub.2 are selected from group
a).
Particularly preferred aminimides are those compounds having the
formula I wherein each R is methyl or ethyl and the lipophilic
radical comprises an aliphatic hydrocarbon chain having from about
10 to about 18 carbon atoms.
As indicated previously, the aminimides of this invention function
as monomeric emulsion stabilizers, which are organic monomers which
stabilize an emulsion of monomers and copolymerize with an
ethylenically-unsaturated monomer, becoming a part of the final
polymer, while stabilizing the polymerization process against the
formation of coagulum and against subsequent phase separation.
Thus, although emulsion polymerization processes can be carried out
without the use of a monomeric emulsion stabilizer by using
conventional surface-active agents, this is undesirable in that it
leads to the presence of a water-sensitive ingredient in the final
polymeric latex.
Illustrative ethylenically-unsaturated monomers suitable for
copolymerizing with the monomeric emulsion stabilizers of this
invention comprise vinyl acetate, vinyl chloride, acrylonitrile,
and acrylic monomers in general represented by the formula ##EQU5##
where R.sub.7 is a hydrogen atom or a methyl group, and R.sub.8 is
an alkyl radical of 1 to 18, and preferably 1 to 10 carbon atoms.
As is known in the art of preparing acrylic ester polymers, the
softness of the polymer and the difficulty of initiating
polymerization may increase as the number of carbon atoms in the
ester group increases. In the practice of this invention, when the
acrylic monomer contains more than 8 carbon atoms in the ester
group, it is advantageous for ease of initiation and polymerization
to mix therewith at least about 20 mole per cent of an acrylic
ester with fewer than 4 carbon atoms in the ester group.
Mixtures of more than one such ethylenically-unsaturated monomer
may be used, and in order to impart special properties of
toughness, rigidity, or cross-linking reactivity to the polymer, a
minor proportion, usually less than 20 mole percent, of the major
monomer may be replaced by some other ethylenically-unsaturated
monomer such as vinyl esters other than vinyl acetate as typified
by vinyl laurate and vinyl stearate; vinyl ethers such as vinyl
methyl ether, vinyl ethyl ether, and vinyl butyl ether;
di-unsaturated monomers such as diethylene glycol diacrylate,
ethylene glycol diitaconate, diallyl phthalate, divinyl benzene and
the like; acrylamide and methacrylamide, hydroxyethyl acrylate and
methacrylate, hydroxypropyl acrylate and methacrylate, and
styrene.
The polymerization process is carried out by emulsion
polymerization techniques, employing a redox or non-redox catalyst
system. Illustrative redox catalyst systems are hydrogen
peroxide/ascorbic acid and ferrous ammonium sulfate, tert-butyl
hydrogen peroxide/ascorbic acid and ferrous ammonium sulfate,
potassium persulfate/sodium bisulfite, potassium persulfate/sodium
metabisulfite, etc. Non-redox catalysts include hydrogen peroxide,
potassium persulfate, etc. Polymerization can be carried out by a
batch loaded technique wherein an emulsion of monomers and
monomeric emulsion stabilizer, prepared by agitating the monomers
and stabilizer in an aqueous medium, is sparged with nitrogen and
then the catalyst system is added to the emulsion. The delayed
addition technique of polymerization can also be used; in an
example of this process using a redox catalyst system, an emulsion
of monomers and monomeric emulsion stabilizer containing the
peroxide or persulfate is prepared. A portion of this emulsion is
added to the reactor along with the ascorbic acid and ferrous
ammonium sulfate, or potassium persulfate respectively. The
remainder of the emulsion is added slowly, usually over a period of
1 hour. The polymerization reactions are initiated at various
temperatures, depending on the catalyst system. Thus, redox systems
are preferably initiated at temperatures of about 0.degree.C to
ambient and non-redox systems at about 50.degree.-60.degree.C.
In general, in the polymerization process of this invention, 1.0 to
30 percent by weight of monomeric emulsion stabilizer is employed,
with 3 to 10 percent by weight being preferred. The amount of
monomeric emulsion stabilizer is based on the total monomers added
to the polymerization reaction; mixtures of monomeric emulsion
stabilizers having the formula I can be employed.
Aqueous polymeric dispersions may be prepared according to this
invention in which the solid polymer content is 40% to 50% by
weight. If desired, the solids content may be diluted to 1% by
weight or less, with excellent retention of stability at both the
higher and lower concentrations. The polymer can be separated from
the polymerization medium by coagulation, e.g. with
isopropanol.
Although the aminimides I of this invention can be used in the
preparation of binders, they are particularly suitable for the
preparation of pressure-sensitive adhesive polymers. In this
embodiment, they are generally copolymerized with an acrylic ester
to provide an excellent thermosetting pressure-sensitive adhesive.
They are readily applied to appropriate flexible backings by
conventional techniques such as casting, calendering etc. Suitable
flexible backings include polyester films, e.g. polyethylene
terephthalate and tensilized polyethylene terephthalate; vinyl
films; polyethylene films; polyethylene-polylpropylene films;
aluminum foil; cloth; laminates of vinyl film and cloth; glass
cloth; non-woven materials; paper; strand-reinforced paper; etc. If
desired, an adhesive priming coat may be applied to the flexible
backing prior to coating with the pressure-sensitive adhesive
composition, but this is not essential to the preparation of
excellent adhesive tapes.
In the following examples, a POLYKEN Probe Tack Tester was used in
determining the probe tack. This apparatus, which is fully
described in U.S. Pat. No. 3,214,971, consists of four functional
parts: (1) a cylindrical steel probe attached to the compression
loaded spring of (2) a Series L Hunter Mechanical Force Gage
(Hunter Spring Company, Brochure 750/FG, revised February 1961),
(3) an annulus having an opening slightly larger than the diameter
of the probe and (4) a carrier for the annulus which moves down to
bring the annulus around the probe and then up to remove the
annulus therefrom. The carrier moves at a speed of 0.1 inch per
second. At the beginning of the test, the carrier is at its
uppermost point of travel, the annulus rests upon the carrier. The
annulus is positioned on the carrier so that the opening in the
annulus is in line with the probe positioned beneath it. A strip of
tape is placed upon the annulus, adhesive surface down, and
spanning the annulus opening. As the carrier is driven downwardly
by a synchronous motor, the adhesive surface exposed through the
opening is brought into contact with the flat surface of the probe.
The tape, and the annulus attached thereto, is suspended on the
probe as the carrier continues further on its downward path. The
carrier then reverses its movement, returning to pick up the
annulus, thereby separating the tape from the probe surface.
Separation begins after one second contact between the probe and
adhesive. The force required to separate the tape from the probe is
recorded on the force gauge. The recorded value is the probe tack
value. Measurements were made employing probes having weights of
10, 100 and 500 gms.
The peel adhesion values are the forces required to remove an
adhesive tape from a stainless steel surface after contact
therewith for 2 minutes at a temperature of about 75.degree.F. The
tape was stripped from the surface at a 180.degree. angle at a rate
of 12 inches per minute.
The creep resistance test is designed to test the resistance of the
adhesive coating to shearing within the plane of the adhesive
coating. A one inch strip of tape is applied to the vertical
stainless steel surface heated to a temperature of about
90.degree.F. A 1 kg. weight is hung from the metal surface. The
failure time is that time at which the tape falls from the
stainless steel surface under the stress applied by the 1 kg.
weight.
Rolling ball tack was determined by securing a piece of the
adhesive tape, adhesive side up, to a horizontal surface. A steel
ball 1/2 inch in diameter is placed on a track, inclined 60.degree.
to the horizontal test surface; the vertical height in inches from
which the ball is released is the first reported value. The ball is
released, and allowed to roll to a stop on the adhesive. The
distance in inches traveled on the adhesive is reported as the
second measurement.
EXAMPLE 1
A. preparation of Monomer
A solution of unsymmetrical dimethyl hydrazine (30 g., 0.5 mole) in
acetonitrile (125 g.) was prepared in a 4-necked, round bottom
flask fitted with a stirrer, condenser, thermometer and two
addition funnels. The solution was heated to 80.degree.C and 89 g.
of a mixture of alkyl chlorides containing approximately 97% decyl
chloride, was added while maintaining the reaction mixture at
81.degree.C. After the completion of the addition, the reaction
mixture was maintained at 80.degree.C for an additional 3 hours.
Then the mixture was allowed to cool to 45.degree.C. A solution of
maleic anhydride (49 g., 0.5 mole) in t-butanol (300 ml.) was added
from one funnel and a solution of sodium methoxide (27 g., 0.5
mole) in dry methanol (250 ml.) was added from the other funnel.
Afer completion of the addition, the reaction mixture was
maintained at 45.degree.C for 3 hours. Then the mixture was allowed
to cool to room temperature, filtered to separate salt and
concentrated to dryness on a thin-film evaporator. The infrared
spectrum of the resulting thick syrup showed aminimide absorption
at 1580 cm.sup.-.sup.1, confirming that
1,1-dimethyl-1-decylamine-4-hydroxymaleoylimide had been
obtained.
B. preparation of Polymer
An emulsion was prepared by blending water (1660 ml.) with 320 g.
of a 50% solution in deionized water of the
1,1-dimethyl-1-decylamine-4-hydroxymaleoylimide prepared in part A,
2-ethylhexyl acrylate (650 g.) and ethyl acrylate (200 g.) in a
4-necked, round bottom flask fitted with paddle stirrer, condenser,
thermometer and nitrogen dispersion tube. The emulsion was cooled
to 12.5.degree.C and sparged with nitrogen for 15 minutes. Then
hydrogen peroxide (20 ml. of three per cent aqueous solution) was
added to the mixture, followed by ascorbic acid (0.3 g.) and
ferrous ammonium sulfate (.021 g.) in 20 ml. of water;
polymerization was initiated soon after the addition, as indicated
by a rise, over 12 minutes, in temperature to 20.degree.C, after
which the polymerization was allowed to proceed for approximately
one-half hour. The resulting polymer was coagulated with
isopropanol to give a tough, grainy crumb. An adhesive tape was
prepared by coating a polyethylene terephthalate film with a
toluene solution of this polymer to a dry thickness of 1.7 mil. The
properties of the resulting pressure-sensitive adhesive are set
forth in the table.
EXAMPLE 2
A. preparation of Monomer
Following the procedure of Example 1,
1,1-dimethyl-1-p-dodecylbenzylamine-4-hydroxymaleoylimide was
prepared from unsymmetrical dimethyl hydrazine (120 g., 2 moles) in
acetonitrile (500 g.), a mixture of alkyl chlorides (590 g., 2
moles), comprising about 95% p-dodecyl benzyl chloride, a solution
of maleic anhydride (190 g., 2 moles) in t-butanol (700 ml.) and a
solution of sodium methoxide (108 g., 2 moles) in dry methanol
(1000 ml.). The infrared spectrum of the product showed aminimide
absorption at 1580 cm.sup.-.sup.1.
B. preparation of Polymer
The amount of 300 g. of a 50% aqueous solution of the
1,1-dimethyl-1-p-dodecylbenzylamine-4-hydroxymaleoylimide prepared
in part A was copolymerized with 2-ethylhexyl acrylate and ethyl
acrylate following the procedure and employing the quantities set
forth in part B in Example 1. The polymer was coated on
polyethylene terephthalate film to a dry mass thickness of 1.4 mil;
the properties of the pressure-sensitive adhesive are listed in the
table.
C. preparation of Polymer
A polymer was prepared utilizing the procedure and reactant amounts
of part B, but substituting butyl acrylate for 2-ethylhexyl
acrylate; the properties of the resulting pressure-sensitive
adhesive are given in the table.
EXAMPLE 3
A. preparation of Monomer
Following the procedure of the preceding examples,
1,1-dimethyl-1-dodecylamine-4-hydroxymaleoylimide was prepared by
reacting unsymmetrical dimethyl hydrazine (30 g., 0.5 mole) in
acetonitrile (125 g.), a mixture of alkyl chlorides (103 g., 0.5
mole) containing about 97% dodecyl chloride, maleic anhydride (49
g., 0.5 mole) in t-butanol (300 ml.) and sodium methoxide (27 g.,
0.5 mole) in dry methanol (250 ml.). Confirmation that the product
had been obtained was indicated by the presence of the aminimide
absorption peak at 1580 cm.sup.-.sup.1 in the infrared
spectrum.
B. preparation of Polymer
A polymer similar to that described in part B of Example 2 was
prepared employing
1,1-dimethyl-1-dodecylamine-4-hydroxymaleoylimide instead of
1,1-dimethyl-1-p-dodecylbenzylamine-4-hydroxymaleoylimide. The
polymerization procedure and reactant amounts described in Example
2 were employed in the preparation of this polymer. The properties
of the resulting pressure-sensitive adhesive, which had a mass
thickness of 2.2 mils when coated on polyethylene terephthalate
film, are listed in the table.
EXAMPLE 4
A. preparation of Monomer
Following the procedure of the preceding examples,
1,1-dimethyl-1-tetradecylamine-4-hydroxymaleoylimide was prepared
by reacting unsymmetrical dimethyl hydrazine (30 g., 0.5 mole) in
acetonitrile (125 g.) with a mixture of alkyl chlorides (118 g.,
0.5 mole) containing about 97% tetradecyl chloride, maleic
anhydride (49 g., 0.5 mole) in t-butanol (300 ml.) and sodium
methoxide (27 g., 0.5 mole) in dry methanol (250 ml.). Aminimide
absorption at 1580 cm.sup.-.sup.1 was observed in the infrared
spectrum of the product.
B. preparation of Polymer
A polymer was prepared utilizing the procedure and reactant amounts
described in part B of Example 2, but employing
1,1-dimethyl-1-tetradecylamine-4-hydroxymaleoylimide (498 g.)
instead of
1,1-dimethyl-1-p-dodecylbenzylamine-4-hydroxymaleoylimide. The
properties of the resulting pressure-sensitive adhesive, when
coated on polyethylene terephthalate film to a thickness of 1.5
mils, are listed in the table.
EXAMPLE 5
A. preparation of Monomer
Following the procedure of the preceding examples,
1,1-dimethyl-1-hexadecylamine-4-hydroxymaleoylimide was prepared by
reacting unsymmetrical dimethyl hydrazine (30 g., 0.5 mole) in
acetonitrile (125 g.) with a mixture of alkyl chlorides (132 g.,
0.5 mole) containing about 97% hexadecyl chloride, maleic anhydride
(49 g., 0.5 mole) in t-butanol (300 ml.) and sodium methoxide (27
g., 0.5 mole) in dry methanol (250 ml.). The infrared spectrum of
the product showed aminimide absorption at 1580 cm.sup.-.sup.1.
B. preparation of Polymer
A polymer was prepared utilizing the procedure and reactant amounts
described in part B of Example 2, but employing
1,1-dimethyl-1-hexadecylamine-4-hydroxymaleoylimide instead of the
aminimide of that example. The properties of the resulting
pressure-sensitive adhesive, which was coated on polyethylene
terephthalate film to a thickness of 2 mils, are listed in the
table.
EXAMPLE 6
A. preparation of Monomer
Following the procedure of the preceding examples,
1,1-dimethyl-1-octadecylamine-4-hydroxymaleoylimide was prepared by
reacting unsymmetrical dimethyl hydrazine (30 g., 0.5 mole) in
acetonitrile (125 g.) with a mixture of alkyl chlorides (144 g.,
0.5 mole) containing 97% octadecyl chloride, maleic anhydride (49
g., 0.5 mole) in t-butanol (300 ml.) and sodium methoxide (27 g.,
0.5 mole) in dry methanol (250 ml.). The infrared spectrum of the
product showed aminimide absorption at 1580 cm.sup.-.sup.1.
B. preparation of Polymer
A polymer was prepared utilizing the procedure and reactant amounts
described in part B of Example 2, but employing
1,1-dimethyl-1-octadecylamine-4-hydroxymaleoylimide as the
aminimide. The properties of the resulting pressure-sensitive
adhesive, which was coated on polyethylene terephthalate film to a
dry thickness of 1.3 mils, are listed in the table.
EXAMPLE 7
A. preparation of Monomer
Following the procedure of the preceding examples,
1,1-dimethyl-1-p-dodecylbenzylamine-4-hydroxycitraconoylimide was
prepared by reacting unsymmetrical dimethyl hydrazine (30 g., 0.5
mole) in acetonitrile (125 g.) with an alkyl chloride mixture 147
g., 0.5 mole) containing about 95% p-dodecylbenzyl chloride
followed by reaction with citraconic anhydride (56 g., 0.5 mole) in
t-butanol (185 ml.) in the presence of sodium methoxide (27 g., 0.5
mole) in dry methanol (250 ml.). Confirmation that the product had
been obtained was indicated by the presence of the aminimide
absorption peak at 1580 cm.sup.-.sup.1 in the infrared
spectrum.
B. preparation of Polymer
Following the procedure of the preceding examples, a
pressure-sensitive polymer was prepared by copolymerizing the
aminimide described in part A (50 g. of a 30% aqueous solution)
with 2-ethylhexyl acrylate (65 g) and ethyl acrylate (20 g.) in the
presence of water (140 ml.), hydrogen peroxide (2 ml. of 3% aqueous
solution) and 3 ml. of aqueous reductant solution containing
ascorbic acid (.03 g.) and ferrous ammonium sulfate (.0021 g.). The
polymer was coated on polyethylene terephthalate film to a dry
thickness of 1.8 mils; the properties of the pressure-sensitive
adhesive are given in the table.
EXAMPLE 8
A. preparation of Monomer
Following the procedure of the preceding examples,
1,1-dimethyl-1-p-dodecylbenzylamine-4-hydroxyitaconoylimide was
prepared by reacting unsymmetrical dimethyl hydrazine 13.3 g.) in
acetonitrile (110 g.) with an alkyl chloride mixture (65.5 g.)
containing 95% p-dodecyl benzyl chloride (65.5 g.) followed by
reaction with itaconic anhydride (25 g.) in t-butanol (220 ml.) in
the presence of sodium methoxide (12.0 g.) in dry methanol (110
ml.). The infrared spectrum of the product showed aminimide
absorption at 1580 cm.sup.-.sup.1.
B. preparation of Polymer
A pressure-sensitive adhesive polymer was prepared following the
procedure and employing the amounts set forth in part B of Example
7, but substituting
1,1-dimethyl-1-p-dodecylbenzylamine-4-hydroxyitaconoylimide for the
aminimide of Example 7. The properties of the resulting
pressure-sensitive adhesive, which was coated on polyethylene
terephthalate film to a dry thickness of 1.7 ml., are given in the
table.
EXAMPLE 9
A. preparation of Monomer
A solution of unsymmetrical dimethyl hydrazine (25.3 g., 0.42 mole)
in acetonitrile (200 ml.) was heated to 80.degree.C and
2-chloroethyl acrylate (50.0 g., 0.42 mole) was added gradually
thereto. The reaction mixture was maintained at 80.degree.C for
five hours and then cooled to 45.degree.C. Following the procedure
of the previous examples, a solution of octadecyl succinic
anhydride (150 g., 0.42 mole) in t-butanol (300 ml.) and a solution
of sodium methoxide (23 g., 0.42 mole) in methanol (300 ml.) was
added and the resulting mixture maintained at 45.degree.C for three
to four hours. After filtration to remove salt, the filtrate was
concentrated to a thin liquid which crystallized to provide 24 g.
of
1,1-dimethyl-1-acryloyloxyethylamine-octadecyl-4-hydroxysuccinylimide,
m.p. 50.degree.C. The infrared spectrum of the product showed
aminimide absorption at 1580 cm.sup.-.sup.1. Analysis. - Calc'd for
C.sub.348 H.sub.54 N.sub.28 O.sub.80 : C, 68.1; H, 10.7; Found: C,
65.78; H, 10.63;
B. preparation of Copolymer
The amount of 5 g. of
1,1-dimethyl-1-acryloyloxyethylamine-octadecyl-4-hydroxysuccinylimide
was dissolved in 73 ml. of water at 60.degree.-70.degree.C with
stirring, and the solution cooled to 10.degree.C. Then 2-ethylhexyl
acrylate (30 g.) and ethyl acrylate (15 g.) were added and the
emulsion sparged with nitrogen for about 30 minutes. Polymerization
occurred upon the addition of 10 ml. of three percent aqueous
hydrogen peroxide, ascorbic acid (1 g.) and ferrous ammonium
sulfate (.07 g.) in 20 ml. water. The polymer was coagulated with
isopropanol, washed, dissolved in toluene and coated on
polyethylene terephthalate film. The dried coating was
pressure-sensitive.
EXAMPLE 10
A. preparation of Monomer
A mixture of glycidyl acrylate (32 g., 0.25 mole) and octadecyl
succinic anhydride (87.2 g., 0.25 mole) in t-butanol (400 ml.) ws
heated, with stirring, at 70.degree.-80.degree.C to dissolve the
anhydride. Then unsymmetrical dimethyl hydrazine (15 g., 0.25 mole)
was added and the reaction mixture was allowed to cool to room
temperature, where it was maintained with stirring for seventy-two
hours. The resulting liquid was concentrated to dryness and
crystallized from isopropanol to provide a waxy, yellow solid,
1,1-dimethyl-1-acryloyloxy-2-hydroxypropylamine-octadecyl-4-hydroxysucciny
limide, m.p. 50.degree.-51.degree.C. The infrared spectrum of the
product showed aminimide absorption at 1580 cm.sup.-.sup.1.
B. preparation of Copolymer
Following the procedure and employing the quantities of Example 9,
part B, a copolymer similar to that of Example 9 was prepared
employing
1,1-dimethyl-1-acryloyloxy-2-hydroxypropylamine-octadecyl-4-hydroxysucciny
limide as the aminimide.
COMPARATIVE EXAMPLE 1
For purposes of comparison, following the procedure described in
Example 1, 1,1-dimethyl-1-octylamine-4-hydroxymaleoylimide was
prepared from unsymmetrical dimethyl hydrazine (60 g., 1.0 mole) in
acetonitrile (250 g.), a mixture of alkyl chlorides (149 g., 1.0
mole) containing about 97% octyl chloride and a solution of maleic
anhydride (98 g., 1.0 mole) in t-butanol (350 ml.) in the presence
of a solution of sodium methoxide (54 g., 1.0 mole) in dry methanol
(500 ml.). Attempts to prepare a copolymer with 2-ethylhexyl
acrylate and ethyl acrylate following the procedure and employing
the reactant amounts described in Example 2, part B were
unsuccessful; no initiation occurred.
COMPARATIVE EXAMPLE 2
For purposes of comparison, following the procedure described in
Example 1, 1,1-dimethyl-1-p-dodecylbenzylamine-acrylimide was
prepared from unsymmetrical dimethyl hydrazine (60 g., 1.0 mole) in
acetonitrile (250 g.), p-dodecyl benzyl chloride (295 g., 1.0 mole)
and a solution of methyl acrylate (86 g., 1.0 mole) in t-butanol
(350 ml.) in the presence of a solution of sodium methoxide (54 g.,
1.0 mole) in dry methanol (500 ml.). Attempts to prepare a
copolymer with 2-ethylhexyl acrylate and ethyl acrylate following
the procedure and employing the reactant amounts described in
Example 2, part B were unsuccessful; no initiation occurred.
COMPARATIVE EXAMPLE 3
For purposes of comparison, following the procedure described in
Example 1, 1,1-dimethyl-1-p-dodecylbenzylamine-methacrylimide was
prepared from unsymmetrical dimethyl hydrazine (60 g., 1.0 mole) in
acetonitrile (250 g.), p-dodecyl benzyl chloride (295 g., 1.0 mole)
and a solution of methyl methacrylate (100 g., 1.0 mole) in
t-butanol (350 ml.) in the presence of a solution of sodium
methoxide (54 g., 1.0 mole) in dry methanol (500 ml.). Attempts to
prepare a copolymer with 2-ethylhexyl acrylate and ethyl acrylate
following the procedure and employing the reactant amounts
described in Example 2, part B were unsuccessful; no initiation
occurred.
Table
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EXAMPLE 1 2(B) 2(C) 3 4 5 6 7 8
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Probe Tack, (gms.) 10 gms. 220 190 250 220 120 200 230 110 150 100
gms. 380 440 370 370 230 230 360 480 370 500 gms. 400 450 360 360
250 300 360 470 420 Adhesion, oz./in. 18.0 17.1 12.0 55.0 11.0 8.0
4.0 68.7 22.1 Creep, hrs. 5.0 1.0 100.0+ <1.0 <1.0 <1.0
>100 .41 73.16 Rolling Ball 6/2.3 6/2.3 6/2.2 6/1.5 6/2.8 6/3.3
-- -- -- Tack, in.
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* * * * *